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Cationic Chain-Growth Polymerization: Mechanism

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...

Step-Growth Polymerization: Overview

Step-Growth Polymerization: Overview

Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...

Molecular Weight of Step-Growth Polymers

Molecular Weight of Step-Growth Polymers

Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...

Radical Chain-Growth Polymerization: Mechanism

Radical Chain-Growth Polymerization: Mechanism

The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into the...

Radical Chain-Growth Polymerization: Overview

Radical Chain-Growth Polymerization: Overview

Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...

Polymers

Polymers

The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the properties that they exhibit. Additionally,...

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La complejidad de la vía en la polimerización supramolecular.

Peter A Korevaar¹, Subi J George, Albert J Markvoort

¹Institute for Complex Molecular Systems, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands.

|January 20, 2012

Resumen

Este resumen es generado por máquina.

Los investigadores observaron la formación de polímeros supramoleculares, revelando dos vías de ensamblaje que compiten entre sí. Mediante el uso de un auxiliar quiral, dirigieron el autoensamblaje hacia una estructura específica y cinéticamente favorecida, demostrando el control sobre la organización molecular.

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Área de la Ciencia:

Se trata de una química supramolecular.
Ciencia de los materiales ciencia de los materiales.
La electrónica orgánica es la electrónica orgánica.

Sus antecedentes:

El autoensamblaje de las moléculas orgánicas es crucial para los materiales funcionales.
Comprender las vías de organización molecular es clave para controlar las propiedades de los materiales.
Los modelos existentes para la formación de fibrillas de proteínas son complejos y se extienden más allá de la simple nucleación.

Objetivo del estudio:

Investigar las vías cinéticas de la formación de polímeros supramoleculares a partir de oligómeros conjugados con π.
Para obtener información cuantitativa sobre el proceso de autoensamblaje.
Para demostrar el control sobre la estructura del ensamblaje final utilizando estímulos externos.

Principales métodos:

Experimentos cinéticos con resolución de tiempo para observar la formación del ensamblaje.
Cálculos de modelos cinéticos para analizar las rutas de competencia.
Autoensamblaje dirigido por auxiliares quirales utilizando ácido tartárico.

Principales resultados:

Identificó un conjunto metastable favorecido cinéticamente que se forma rápidamente.
Reveló dos vías de autoensamblaje paralelas y competidoras con helicidad opuesta.
Demostró que un auxiliar quiral puede favorecer selectivamente la vía controlada cinéticamente.

Conclusiones:

El autoensamblaje de los oligómeros conjugados π implica complejas vías cinéticas.
Los auxiliares quirales se pueden utilizar para controlar con precisión el resultado termodinámico del autoensamblaje.
Esto proporciona un método para obtener ensamblajes supramoleculares metastables bajo demanda.